Carbamoylphosphonates

ABSTRACT

This disclosure teaches a method for employing novel carbamoylphosphonates such as ammonium ethyl carbamoylphosphonate, ammonium isopropyl carbamoylphosphonate and ammonium allyl carbamoylphosphonate to regulate the growth rate of plants.

United States Patent [191 Langsdorf [451 Nov..5, 1974CARBAMOYLPHOSPHONATES [75] Inventor: William P. Langsdori, Wilmington,

Del.

260/239 B, 260/239 EP, 260/247.7 P,

260/429.9, 2 60/294l7 A, 260/923, 260/924 [51] Int. Cl. C071 9/40, A01n5/00 [58] Field of Search 260/943 [56] References Cited UNITED STATESPATENTS 3,005,010 10/1961 Grisley ..260/943X Primary ExaminerAnton H.Sutto [57] ABSTRACT This disclosure teaches a method for employing novelcarbamoylphosphonates such as ammonium ethyl carbamoylphosphonate,ammonium isopropyl carbamoylphosphonate and ammonium allylcarbamoylphosphonate to regulate the growth rate of plants.

5 Claims, No Drawings CROSS REFERENCE TO RELATED APPLICATIONS Thisapplication is a continuation-in-part of my copending application Ser.No. 85,221, filed Oct. 29, 1970, which is a continuation-in-partof myapplication Ser. No. 803,962, filed Mar. 3, 1969, now abandoned, whichwas in turn a continuation-in-part of my earlier application Ser. No.731,732, filed May 24, 1968, now US. Pat. No. 3,627,507.

BACKGROUND OF THE INVENTION This invention relates to the discovery thata selected group of novel carbamoylphosphonates can be used to regulatethe growth rate of plants. More particularly, the compounds of thisinvention are useful for controlling the growth of woody vegetation.

Related compounds such as the dialkyl carbamoylphosphonates aredisclosed in U.S. Pat. No. 3,005,010 as herbicides.

SUMMARY OF THE INVENTION In summary, this invention relates to a novelgroup of carbamoylphosphonates, the method of using thecarbamoylphosphonates to regulate the growth rate of plants andformulations containing carbamoylphosphonates which are useful toregulate the growth rate of plants.

More particularly, the 'carbamoylphosphonates of this invention arerepresented by the formula:

wherein:

R is alkyl of one through six carbon atoms,chloroalkyl of one throughsix carbon atoms containing up to three chlorine atoms, bromoalkyl ofone through six carbon atoms containing up to three bromine atoms,alkoxy alkyl of three through seven carbon atoms, alkenyl of two throughsix carbon atoms, alkynyl of three through four carbon atoms, phenyl orbenzyl;

R is hydrogen or methyl;

R is hydrogen, methyl, amino, methylamino, or dimethylamino;

R and R; can be taken together to form a ring selected from (CH O(CH or(CH where n is 2-6;

M is selected from the group consisting of ammonium, hydrogen, sodium,lithium, potassium, calcium, magnesium, zinc, manganese, barium or whereR R and R; can be the same or different and each can be hydrogen, alkylof one through four carbon atoms, or hydroxy alkyl of two through fourcarbon atoms; and R is hydrogen, alkyl of one through 12 carbon atoms,allyl, benzyl, amino, methylamino, or dirnethylamino; R and R, can betaken together to form a riiig that is (CI-I2);

and R and R are H.

Preferred compounds of this invention include those compounds of formula(1) where R is alkyl of one through four carbons or alkenyl of threethrough four carbons; R and R are each hydrogen; and M is ammonium,hydrogen, or alkali metal such as sodium, lithium or potassium.

The most preferred compounds of this invention are ammonium allylcarbamoylphosphonate, ammonium ethyl carbamoylphosphonate, and ammoniumisopropyl carbamoylphosphonate.

Another aspect of this invention relates to the method for modifying thegrowth rate of plants which comprises applying an effective amount of acompound of formula (1) to a plant to effect modification of the growthrate of said plant. Specifically, the method of this invention resultsin retarding the growth rate of the treated plants.

Another aspect of this invention relates to fonnula-' tions of compoundsof formula (1) with suitable agricultural adjuvants and modifiers orwith tree wound dressings.

DESCRIPTION OF THE INVENTION formula l are particularly useful to retardthe growth rate of plants without killing them. The compounds of thisinvention are particularly useful to retard the growth of woody plants.The compounds of this invention can, therefore, be applied in areas suchas power line rights-of-way where low-growing and slow growingvegetation is especially desirable.

In addition to their value as plant growth retardants the compounds ofthis invention can also be used to, control flowering, fruit set andcoloration on apples and other fruits. They are useful to control thegrowth and flowering of ornamental species such as chrysanthemum andazalea.

The compounds of this invention can also be used to prolong the dormancyof perennial plants, and thereby protect the unsprouted buds from frostdamage. This can be especially important in the protection of flowerbuds, which in some years, may sprout early and be killed by coldtemperatures.

PREPARATION diesters of carboalkoxyphosphonic acids with aqueoussolutions of ammonia, primary amines or secondary amines.

This reaction can be considered to occur in two steps as is illustratedby the following equations.

In equations (2) and (3) R is alkyl of one through six carbon atoms,chloroalk-yl of one through six carbon atoms containing up to threechlorine atoms, bromoalkyl of one through six carbon atoms containing upto three bromine atoms, alkoxy alkyl of from three through seven carbonatoms, alkenyl of two through six carbon atoms, alkynyl of three throughfour carbon atoms, phenyl or benzyl; R is alkyl of one through fourcarbon atoms, preferably methyl or ethyl; R is alkyl of one through sixcarbon atoms, chloroalkyl of one through six carbon atoms containing upto three chlorine atoms, bromoalkyl of one through six carbon atomscontaining up to three bromine atoms, alkoxy alkyl of three throughseven carbon atoms, alkenyl of two through six carbon atoms, alkynyl ofthree through four carbon atoms,'phenyl or benzyl; R is hydrogen or.methyl; R is hydrogen, methyl, amino, methylamino, or dimethylamino; Rand R can be taken together to form a ring selected from (CH O(CH or(CH2)1| where 'n is 2-6; M is selected from the group consistingofammonium, hydrogen, sodium, lithium,.potassium, calcium, magnesium,zinc, manganese, barium or where R R and R can be the same or differentand each can be hydrogen, alkyl of one through four carbon atoms, orhydroxy alkyl of two through four carbon atoms; and R is hydrogen, alkylof one through 12 carbon atoms, allyl, benzyl, amino, methylamino, ordimethylamino; R and R can be taken together to form a ring that is -(CHO-(CH or -(CH where n is 2-6 and R and R are H.

The synthesis method, exemplified by equations (2) and (3) involvesconcurrent or consecutive aminolysis and hydrolysis of the startingdialkyl carboalkoxyphosphonate by interaction with water and the aminereactant.

While equations 2) and (3) represent the route predominantly taken bythe reaction when combined in one operation, some hydrolysis may occurduring or before aminolysis. However, the postulated reaction sequenceas represented by equations (2) and (3) favoring formation of thecarbamoyl-phosphonate intermediate isproved experimentally, as it ispossible in some instances to isolate the carbamoylphosphonateintermediate shown as the product of equation (2). It has, of course,also been experimentally demonstrated that the product of equation (3)is in fact obtained.

An alternate method for synthesis of those compounds of this inventionwhere R is substituted by chlorine or bromine consists of the additionof halogen or hydrogen halide to'the double bond of the compounds ofthis invention where R is alkenyl. This reaction is illustrated byequation (4).

The dialkyl carbamoylphosphonates prepared as described above or bymethods described in the chemical literature are readily hydrolized tothe monoester salt compounds of this invention by addition to aqueousammonia or amine solutions. This procedure may be used therefore toobtain a mixed product, comprising a salt of one amine and an amide ofanother. This will be discussed and exemplified below.

The dialkyl carboalkoxyphosphonates and dialkyl carbamolyphosphonatesused for the synthesis of the compounds of this invention can beprepared by methods available in the literature, such as Nylen, Chem.Ber. 57, 1023 (1924) and Reetz et al., J.A.C.S. 77, 3813-16 1955) usingappropriate ester intermediates.

Generally, the alkoxy group of the carboalkoxyphosphonate is limited forpractical purposes to methyl and ethyl, since there appears to be noadvantage to increasing the size of the alcohol moiety. However, higheralcohol derivatives are useful in some instances.

The following are illustrative of typical diesters of thecarboalkoxyphosphonates:

Diethyl carbomethoxyphosphonate Diallyl carbomethoxyphosphonateDiisopropyl carboethoxyphosphonate Dibutyl carbobutoxyphosphonateDimethallyl carboethoxyphosphonate The following are illustrative oftypical carbamoylphosphonate esters;

Diethyl carbamoylphosphonate Diallyl N,N-dimethylcarbamoylphosphonateDiallyl carbamoylphosphonate Dipropyl N-methylcarbamoylphosphonatDimethyl piperidinocarbonylphosphonate Bis( 2-chloroethyl)carbamoylphosphonate The following are illustrative of the amines whichcan be used for the amination and/or hydrolysis of the esters:

Ammonia Methylamine Dimethylamine Allylamine Propylamine EthylamineMorpholine Piperidine Methylhydrazine N,N-Dimethylhydrazine EthanolamineMore particularly, in the preferred procedure for preparing the ammoniumalkyl carbamoylphosphonates of this invention, a dialkylcarboalkoxyphosphonate or dialkyl carbamoylphosphonate is added to astirred'aqueous solution of ammonia or other amine.

Stirring is'continued until a clear solution is obtained. The resultantsalt can then be isolated by removal of the water through evaporation orby stripping under reduced pressure. In general, these salts are stablewhite crystalline solids or viscous liquids. Those which are solid canbe recrystallized from one or a mixture of several lower alcohols.However, most of the products are suitable for use without purification.

It is preferred that an excess of ammonia or amine be employed in thisreaction to insure good yields and rapid reaction. A ratio of diester toamine of 1 to 2 or greater is employed. Preferably the ratio of diesterto amine of between 1 to 2'and 1 to is employed. The excess amineinsures that amidation of the carboxylic ester rather than hydrolysis isthe predominant reactron.

It is also preferred that a concentration of ammonia or amine of from to50 percent be employed, although the reaction can be operated at higheror lower concentrations.

When the amine reactant is not highly soluble in water, another solvent,such as methanol or ethanol can be added to the aqueous system tosolubilize the amine reactant and thereby increase its reactivity.

This process can conveniently be carried out at about room temperature,although higher temperatures can also be employed if it is desired tospeed up the rate of reaction. This process is moderately exothermic,and therefore must .be controlled by regulation of the diester additionrate and/or by external cooling to maintain the desired temperature.

- A highly satisfactory procedure is to slowly add thediester to astirring aqueous solution of the amine and alkaline earth metals byinterchanging the ammonium salt with appropriate bases or salts.

Another method is to convert the ammonium salt to the free acid, andthen neutralize the free acid with the appropriate base or salt.

The following illustrative examples are presented to further illustratethis invention. In the following examples, parts and percentages are byweight unless otherwise specified.

EXAMPLE 1 C. and stirring is continued for 2 hours. The clear solutionis stripped under reduced pressure (15 mm of Hg) at a water-bathtemperature or 70C. The residue is a white crystalline solid which isrecrystallized from absolute ethyl alcohol, giving 12.3 parts ofammonium allyl carbamoylphosphonate, m.p. l60-162.5C. Nonaqueoustitration either as an acid or a base gives a molecular weight of182121.

EXAMPLES 2-9 The procedure of Example 1 is repeated by substituting anequivalent amount of the indicated Phosphonate Ester for the diallylcarbomethoxyphosphonate of Example 1 to produce the indicated SaltProduct.

Ex. Phosphonate Ester Salt Product 2 diethyl carboxymethoxy hosphonateammonium eth l carbamoylphosphonate m.p. 173-176 3bis(2-chloroethyl)carbo utoxyphosammonium 2-c1oroethylcarbamoylphosphonate, mp. 117-120 phonate 4 dibutylcarboethoxyphosphonate ammonium butyl carbamoylphosphonate m.p.205.5-2065 5 diallyl carboethoxyphosphonate ammonium allylcarbamoylphosphonate 6 dimethallyl carbomethoxyphosphonate ammoniummethallyl carbamoylphosphonate, mp. 193-197 7 diisopropylcarboethoxyphosphonate ammonium isopropyl carbamoylphosphonate, mp.213-216 (dec.)

8 diemethyl carbomethoxyphosphonate ammonium methylcarbamoylphosphonate, mp. 148-151 9 dipropyl carbopropoxyphosphonateammonium propyl carbamoylphosphonate, mp. 190-192 (dec.) 10 diisobutylcarbomethoxyphosphonate ammonium isobutyl carbamoylphosphonate, mp.221-222 (dec.) 1 1 dihexyl carbomethoxyphosphonate ammonium hexylcarbamoylphosphonate,m.p. 212 (dec.)

12 bis( lethyl-2-butenyl)carbomethoxyammonium(1-ethyl-2-butenyl)carbamoylphosphonate phosphonate '13bis(2-methoxyethyl)carbomethoxyammonium Z-methoxyethylcarbamoylphosphonate phosphonate 14bis(2-bromopropyl)carbomethoxyphosammonium 2'bromopropylcarbamoylphosphonate honate 15 is(6-chlorohexyl)carbomethoxyphosammonium6-chlorohexyl carbamoylphosphonate phonate 16bis(6-brom0hexyl)carbomethoxyphosammonium fi-bromoliexylcarbamoylphosphonate phonate l7bis(2-butoxyethyl)carbomethoxyphosammonium 2-butoxyethylcarbamoylphosphonate, hydgroscopic solid phonate l8bis(2,2,2-trichloroethyl)carbomethoxyammonium2,2,2-tnchloroethylcarbamoylphosphonate hosphonate 19is(2,2,2-tribromethyl)carbomethoxyammonium2,2,2-tribromoethylcarbamoylphosphonate phosphonate which is cooled andmaintained at about 15C. When addition of the diester is complete, thetemperature of the mixture is allowed to come to room temperature orslightly above. Generally, the reaction is complete in a few minutes toseveral hours depending on the reactants and conditions used.

The ammonium salts prepared as described above can be converted to saltsof other bases or of alkaline EXAMPLE 20 To a stirring ice-chilledsolution of parts percent methylamine in water is added slowly 8.4 partsof dimethyl carbomethoxyphosphonate. Thev mixture is warmed to 25C. andallowed to stir for 3 hours. The clear solution on stripping underreduced pressure yields 9.6 parts methylammonium methylN-methylcarbamoylphosphonate as a colorless ,oil. The product analyzesfor the dihydrate.

EXAMPLES 21-27 of the indicated SaltProducts are isolated as liquids orlow melting solids.

Ex. Aqueous Amine Phosphonate Ester Salt Product 21 methylamine Idiethyl methylam- (40%) carboethoxyphosphonmonium ethyl ateN-methylcarbamoylphosphonate 22 methylamine diisoporpyl methylam- (40%)carbomethoxyphosmonium phonate isopropyl N-methylcarbamoylphosphonate 23methylamine diallyl methylam- (40%) carbethyxyph0sphon monium allyl ateN-methylcarbamoylphosphonate 24 dimethyalminediethylcarbomethoxydimethylam- (25%) phosphonate monium ethylN,N-dimethylcarbamoylphosphonate 25 methylhydrazine diethyl methyl 0%)carboe thoxyphosphoncarbazoylphosate phonic acid,

monoethyl ester, salt with methyl hydrazine 26 pipcridine (50%) dibenzylpiperidinium carbomethoxyphosbenzyl phonate piperidinocarbonylphosphonate Y 27 l,l-dimethylhydradipropyl l,l-dimethylhyzine (35%)carbomethoxyphosdrazinium propyl phonate3,3-dimethylcarbazoylphosphonate EXAMPLE 28 Eight parts'of diethylN-methylcarbamoylphosphonate is added slowly to 18 parts of a 29 percentaqueous solution of ammonia, while holding the temperature at 25C. byexternal cooling. The unreacted ammonium hydroxide is allowed toevaporate, giving a white, crystalline, solid residue. Recrystallizationfrom absolute ethanol gives 5 parts of ammonium ethylN-methylcarbamoylphosphonate, mp. 189C.

EXAMPLES 29-41 the diethyl methylcarbamoylphosphonate of Example 28 toobtain the indicated Salt Product.

Ex. Aqueous Amine Phosphonate Ester Salt Products ammonium phenylN-methyl carbamoylphosphon ate 29 ammonia diphenyl N-methylcarbamoylphosphonate -Continued Ex. Aqueous Amine Phosphonate Ester SaltProducts 30 methylamine dimethyl N,N-dimethyl methylam- (25%)carbamoylphosphonate monium methyl N,N-dimethylcarbamoylphosphonatate 31diemtylamine diethylcarbamoylphosdimethylam- (25%) phonate monium ethylcarbamoylphosphonate 32 allylamine (25%) diallyl allylammoniumcarbamoylphosphonate allyl carbam'oylphosphonate 33 isobutylaminediisopropyl N-methyl' isobutylam- (20%) carbamoylphosphonate moniumisopropyl N-methylcar- I bamoylphosphonate 34 methylamine diisopropylmethylam- (20%) morpholino'carbonylmonium phosphonate isopropylmorpholinocarbonylphosphonate 35 triethanolamine diallyltriethanolamcarbamoylphosphonate monium allyl carbarn0ylphosphonate 36ammonia (29%) diethyl ammonium ethylpyrrolidinocarbonylpyrrolidinocarphosphonate bamoylphosphonate, mp.189-192 (dec.)

37 ammonia (29%) diethyl ammonium ethylmorpholinocarbonylmorpholinocarphosphonate bonylphosphonate, mp. 183-185i (dec.)

38 ammonia (29%) diethyl ammonium ethyl N,N-dimethylcar-N,N-diemthylcarbamoylphosphonate bamoylphosphonate, m.p.

39 ammonia (29%) bis(3-butynyl)N,N-. ammonium dimethylcarbamoyl-3'butynyl phosphonate N,N dimethylcarbamoylphosphonate 40 ammonia (29%)diethyl ammonium ethyl N-methylcarbamoyl- N-methylcarphosphonatebamoylphosphonate 4l ammonia diethyl ammonium ethylaziridiniumcarbamoylaziridiniumcarphosphonate bamoylphosphonate EXAMPLE42 EXAMPLES 43-44 The procedure of Example 42 is repeated substitutingan equivalent amount of the indicated Alkenyl Reagent for the ammoniumallylcarbamoylphosphonate of Example 42 and an equivalent amount of theindicated Halogen for the bromine of Example 42 to obtain the indicatedProduct.

ammonium methallyl 43 chlorine ammonium carbamoylphosphonate2,3-dichloro-2- methylpropyl carbamoylphosphonate 44 ammonium but-Z-enylbromine ammonium carbamoylphosphonate 2,3-dibromutylcarbamoylphosphonate EXAMPLE 45 An aqueous solution of 45 parts ammoniumhydroxide is stirred and chilled with an ice bath, while 24.4 partsbenzyl methyl carbomethoxyphosphonate is added slowly. Stirring iscontinued until a clear solution is obtained. Unreacted ammoniumhydroxide and water are removed from the mixture under reduced pressure,leaving as a solid residue ammonium monobenzyl carbamoylphosphonate, mp.186, after recrystallization from ethanol.

EXAMPLES 46-5 1 The procedure of Example 45 is repeated substituting anequivalent amount of the indicated Aqueous Amine for the ammoniumhydroxide of Example 45 and an equivalent amount of the indicatedPhosphonate Ester for the benzyl methyl carbomethoxyphosphonate ofExample 45 to obtain the indicated Salt Product as a principal productof this procedure.

To a stirring suspension of 21.2 parts ammonium butylN-methylcarbamoylphosphonate and 100 parts methanol is added 42 parts ofa 40 percent solution of N-benzyltrimethylammonium hydroxide inmethanol. Ammonia and methanol are stripped from the mixture at 40C.under reduced .pressure, leaving benzyltrimethylammonium butyl-N-methylcarbomoylphosphonate as a residue.

EXAMPLES 53-56 The procedure of Example 52 is repeated substituting anequivalent amount of the indicated Base for theN-benzyltrimethylammonium hydroxide of Example 52 and an equivalentamount of the indicated Ammonium Phosphonate for the ammonium butylN-methylcarbamoylphosphonate of Example 52 to obtain the indicated SaltProduct.

Ammonium Ex. Base Phosphonate Salt Product 53 tetraethylammonium allyltetraethylammonium ammonium carbamoylphosmonoallyl hydroxide phonatecarbamoylphosphonate 54 trimethylamammonium ethyl trimethylammonium ine(large N methylcarmonoethyl excess) bamoylphosphon-N-methylcarbamoylphosate phonate 55 ethanolamine ammoniumethanolammonium methallyl methallylhexahydroazepinohexahydroazepinocarcarbonylphos bonylphosphonate phonate56 benzylamine ethylammonium benzylammonium isopropyl isopropylcarbamolyphoscarbamoylphosphonate phonate EXAMPLE 57 A 5 percent aqueoussolution of ammonium ethyl carbamoylphosphonate is passed through apacked column of sulfonated polystyrene copolymer hydrogentype resin toconvert the salt to the free acid. Evaporation of the water gives aresidue of the acid ester, ethyl carbamoylphosphonic acid, mp. C.

EXAMPLES 58-60 The procedure of Example 57 is repeated, first obtainingthe indicated Acid Ester in aqueous solution and then removing the waterto obtain the water-free product, usually a solid.

Ex. Ammonium Phosphonate Acid Ester 58 ammonium methyl methylN-methylcarbonylphosphonate N-methylcarbamoylphosphonic acid 59 ammoniumisopropyl isopropyl carbamoylphosphonate carbamoylphosphonic acid 60ammonium alkyl alkyl carbamoylphosphonate carbamoylphosphonic acidEXAMPLE 61 A 5 percent aqueous solution of ammonium propylN-methylcarbamoylphosphonate is passed through a packed column ofsulfonated polystyrene copolymer hydrogen type resin to convert the saltto the free acid.

This is neutralized with the equivalent amount of so-.

dium bicarbonate to give a solution of essentially pure sodium propylN-methylcarbamoylphosphonate. Evaporation of this solution gives thesolid salt product.

EXAMPLES 62-75 The procedure of Example 61 is repeated, first obtainingthe free acids of the indicated gAmmonium Phosphonate as was done inExample 1" and then neutralizing the acid with the indicated Baseaccording to the procedure of Example 61 to obtain the indicated SaltProduct.

Ammonium Ex. Phosphonate Base Salt Product 62 ammonium sodiumbicarbonate sodium phenyl phenyl carbamoylphosphoncarbamoylphosatephonate Bicarbonate Salt Salt Product sodium bicarbonate potassiumbicarbonate tetramethylammonium bicarbonate benzyltrimethylammoniumsodium ethyl N methylcarbamoylphosphon ate potassium benzylcarbamoylphosphonate tetramethylammonium allylpiperidinocarbonylphosphonate benzyltrimethylammonium butyl bicarbonatephonate carbamoylphosphonate Continued Ammonium Ex. Phosphonate BaseSalt Product 63 ammonium calcium hydroxide hemicalcium benzyl benzylcarbamoylphosphon carbamoylphosate phonate 64 ammonium ethyl bariumhydroxide hemibarium ethyl carbamoylphoscarbamoylphosphonphonate ate 65ammonium hydroxyethhydroxyethmethyl-N,N-yltrimethylamyltrimethylammonium dimethylcarmonium hydroxide methylbamoylphos- N,N-dimethylcarphonate bamoylphosphonate 66 ammoniumbenzyltrimethylambenzyltrimethylambenzyl monium hydroxide monium benzylcarbamoylphoscarbamoylphosphom phonate ate 67 ammonium allyl magnesiumhemimagensium allyl carbamoylphoshydroxide carbamoylphosphonphonate ate68 ammonium butyl morpholine morpholinium butyl N-mcthylNmethylcarbamoylcarbamoylphosphosphonate phonate 69 ammoniumtrimethylamine trimethylammonium monoisopropyl isopropyl morpholinemorpholino-carcarbonylphosphonate bonylphosphonate 70 ammonium ethyltetrabutylammonium tetrabutylammonium carbamoylphoshydroxide ethylphonate carbamoylphosphonate, hygroscopic solid 71 ammonium ethyllithium carbonate lithium ethyl carbamoylphoscarbamoylphosphonphonateate, m.p. above 300C. 72 ammonium ethyl zinc carbonate hemizinc ethylcarbamoylphoscarbamoylphosphonphonate ate, m.p. 244 (dec.) 73 ammoniumdodecylamine dodecylammonium isopropyl isopropylcarbamoylphoscarbamoylphosphonphonate ate 74 ammonium allyl manganoushemimanganous allyl carbamoylphoscarbonate carbamoylphosphonphonate ate75 ammonium butyl dodecyltrimethyldodecyltrimethylammorpholinumcaammonium monium butyl rbonylphoshydroxidemorpholiniumcarphonatc bonylphosphonate EXAMPLE 76 To a stirred solutionof parts of potassium bicarbonate and 50 parts of water is added 18.4parts ammonium isobutyl carbamoylphosphonate. Stirring is continueduntil solution is complete. The solution is evaported to dryness, givingthe solid product, potassium isobutylcarbamoylphosphonate.

EXAMPLES 77-80 The procedure of Example 76 is repeated substituting theindicated Bicarbonate Salt for the potassium bicarbonate of Example 76and an equivalent amount of the indicated Carbamoylphosphonate for theammonium monoisobutyl carbamoylphosphonate of Example 76 to obtain theindicated Salt Product.

Formulation Plant growth modifying compositions of the present inventioncan be prepared by admixing at least one of the compounds of thisinvention with pest control adjuvants or modifiers to providecompositions in the form of dusts, water-soluble powders, solutions,granules or pellets. In addition, the plant growth modifying agents suchas maleic hydrazide and Alar (N-dime thylaminosuccinamic acid) can beincluded in the compositions of this invention in combination with thecompounds of this invention.

Compositions of the invention, may contain as a conditioning agent oneof more surface-active agents, sometimes called surfactants, in amountssufficient to render a given composition containing the compounds ofthis invention readily soluble in water or capable of wetting foliageefficiently.

The surface-active agent used in this invention can be a wetting,dispersing or an emulsifying agent which will assist dispersion andsolution of the active compound. The surface-active agent or surfactantcan include such anionic, cationic and non-ionic agents as haveheretofore been generally employed in plant control compositions ofsimilar type. Suitable surface-active agents are set forth, for examplein Detergents and Emulsifiers 1967 Annual by John W. McCutcheon, lnc.

In general, less than 10 percent by weight of the surface-active agentwill be used in compositions of this invention and ordinarily the amountof surface-active agents will range from 1-5 percent but may even beless than 1 percent by weight.

Additional surface-active agents can be added to the formulations toincrease the ratio of surfactantzactive ingredient up to as high as 5:1by weight. Such compositions may have a greater effectiveness than canbe expected from a consideration of the activity of the components usedseparately. When used at higher rates, it is preferred that thesurfactant be present in the range of one-fifth to five parts surfactantfor each one part of active agent.

The classes of extenders suitable for the watersoluble powderformulations of this invention are the natural clays, diatomaceousearth, synthetic mineral fillers derived from silica and silicate,starch, sugar, and inorganic salts. Most preferred fillers for thisinvention are kaolinites, attapulgite clay, montmorillonite clays,synthetic silicas, synthetic magnesium silicate, calcium sulfatedihydrate, and disodiuin hydrogen phosphate.

Suitable surfactants for use in such compositions are those listed by J.W. McCutcheon in Detergents and Emulsifiers 1967 Annual. Among the morepreferred surfactants are the non-ionic and anionic type, and

those most suitable for the preparation of the dry, soluble products ofthis invention are solid forms of com- Wetting and dispersing agents inthese preferred water-soluble compositions of this invention are usuallypresent at concentrations of from about 0.5 weight percent to 5 weightpercent. The inert extender then completes the formulation. Whereneeded, 0.1 weight percent to 1.0 weight percent of the extender may bereplaced by a corrosion inhibitor or an anti-foaming agent or both.

Thus, water-soluble formulations of the invention will contain fromabout to 95 weight percent active material, from 0.5 to 2.0 weightpercent wetting agent, from 0.25 to 5.0 weight percent dispersant, andfrom 4.25 to 74.25 weight percent inert extender, as these terms aredescribed above.

When the water-soluble powder contains a corrosion inhibitor or ananti-foaming agent or both, the corrosion inhibitor will not exceedabout l-percent of the composition, and the anti-foaming agent will notexceed about 0.5 percent by weight of the composition, both replacingequivalent amounts of the inert extender.

Solution Concentrates The aqueous solution concentrates are prepared bymixing a water-soluble active compound of this invention with water. Aportion of the water may be replaced with methanol, ethanol,isopropanol, ethylene glycol, cellosolve or methyl cellosolve.Surfactants and buffering agents can optionally be present.

These aqueous solution concentrates will contain from 15 to 60 percentof active ingredient, and from 40 to 85 percent water or mixture ofwater and hydroxylated organic solvent. Surfactants, corrosioninhibitors, buffering and anti-foam agents may also be included in whichcase they may replace up to 10 percent of the solvent system.

Dusts Dusts are dense powder compositions which are intended forapplication in dry form, inaccordance with the preferred compositionsand methods of the invention. Dusts are characterized by theirfree-flowing and rapid settling properties so that they are not readilywindborne to areas where their presence is not desired. They containprimarily an active material and a dense, free-flowing, solid extender.

Their performance is sometimes aided by the inclusion of a wettingagent, and convenience in manufacture frequently demands the inclusionof an inert, adsorptive grinding aid. For the dust compositions of thisinvention, the inert extender may be either of vegetable or mineralorigin, the wetting agent is preferably anionic or non-ionic andsuitable adsorptive grinding aids are of mineral origin.

Suitable classes of inert solid extenders for use in the dustcompositions are those organic or inorganic powders which possess highbulk density and are very freeflowing. They are also characterized bypossessing relatively low surface areas and are poor in liquidadsorption. Suitable classes of grinding aids are natural clays,diatomaceous earths, and synthetic mineral fillers derived from silicaor silicate. Among ionic and non-ionic wetting agents, the most suitableare the members of the group known to the art as wetting agents andemulsifiers. Although solid agents are preferred because of ease inincorporation some liquid non-ionic agents are also suitable in the dustformulations.

Preferred inert solid extenders for the dusts of this invention aremicaceous tales, pyrophyllite, dense kaolin clays, tobacco dust andground calcium phosphate rock such as that known as Phosphodust," atrademark of the American Agricultural Chemical Company.

Preferred grinding aids are attapulgite clay, diatomaceous silica,synthetic fine silica and synthetic calcium and magnesium silicates.Preferred wetting agents are those previously described underwater-soluble powder formulations. The inert solid extenders in thedusts of this invention are usually present in concentrations of fromabout 30 to weight percent of the total composition. The grinding aidwill usually constituteS to 50 weight percent of the composition, andthe wetting agent will constitute from about 0 to 1.0 weight percent ofthe composition. Dust compositions can also contain other surfactantssuch as dispersing agents in concentrations of up to about 0.5 weightpercent.

The water-soluble powders described above can also be used in thepreparation of dusts. While such watersoluble powders could be useddirectly in dust form, it is more advantageous to dilute them byblending with the dense dust diluent. In. this manner, dispersingagents, corrosion inhibitors, and anti-foam agents may also be found ascomponents of a dust.

Thus,- the dust compositions of this invention will comprise about 5 to20 weight percent active material, 5 to 50 weight percent adsorptivetiller, 0 to 1.0 weight percent wetting agent, and about 30 to 90 weightpercent dense, free-flowing dust diluent, as these terms are usedherein. Such dust formulations can contain, in addition, minor amountsof dispersants, corrosion inhibitors, and anti-foam agents, derived fromthe watersoluble powders used to make the dusts.

Granulesand Pellets Under some circumstances it may-be advantageous Onemethod of preparation suitable for both granules and pellets involvesblending the active ingredient with clays, water-soluble salts,surfactants and a small amount of water. After pelleting and/orgranulating,

the formulation is dried prior to use. A second method suitable for thepreparation of granules formulation involves spraying a solution of theactive material on porous, adsorptive, preformed clay or vermiculitegranules. Surfactants listed by McCutcheon can also be included in thespray solution. After drying, the granules are ready for application.

The preferred granules or pellets will contain about 5 to 30 weightpercent of active material, about to weight percent wetting agent andabout 65 to 95 weight percent inert mineral carrier.

paints. At the low levels employed (1 5 percent),

there is generally little effect on the physical properties of thesystems, and commercial materials need not be reformulated. Atrelatively high levels, the active ingreclient, being a salt can causeconventional emulsions to thicken or break. In the former case meredilution with water is effective to restore physical properties; in thelatter case. a salt-tolerant emulsifier must be selected.

As the compounds of formula (1) have rather low solubility in organicsolvents, they must be finely ground and well dispersed to be effectivein systems such as solvent-based varnishes and paints. In such systems,the active ingredient must be treated as a pigment would be.Additionally, water must be rigorously excluded, otheriwse the activematerial will not remain well-dispersed.

When packaged as an aerosol, similar considerations apply. The preferredtype of formulation is an emulsion with the compound of formula (1) inthe aqueous phase and the film former, solvent and propellant system inthe organic phase. Dispersions in organic systems are possible but notpreferred becausev of difficulty in assuring adequate-mixing before use,the need to-rigorously exclude moisture, and the expense of assuring anadequately tine particle size.

Application As stated earlier, this invention is founded on thediscovery that the compounds of formula (1) are useful for modifying thegrowth rate of plants. More particularly the compounds of this inventionare useful as plant growth retardants. They also affect the floweringand fruit set of numerous plants.

The term plant growth retardant as used in this disclosure is to beunderstood to mean an agent which when applied to a plant or itsenvirons will slow the growth of the plant without killing or causingextensive injury to said plant. This also includes a delaying responseon bud sprouting or prolonging of the dormancy period.

The compounds of this invention can be used to retard bud break and thegrowth of woody vegetation.

The compounds of this invention can also be used to control the growthof turf and other herbaceous vegetations.

The compounds of this invention can be applied as foliar sprays or assoil applications to retard the growth rate of such plants or to affectflowering and fruit'set.

Preferably, the compounds of this invention are applied as a foliarspray to the point of runoff although lower-volume application may alsobe effective.

It is preferred that the application be made a short time prior to theperiod when maximum plant growth is anticipated, but application canalso be made during the dormant stage or just after the plants have beentrimmed. Or if flowering and fruit set are to be modified, the treatmentis applied before, during, or shortly after flowering.

To prevent bud break it is preferred that the application be made at thetime the buds for the next year are being developed. For most plantsthis is from July to a few weeks before leaf-fall.

It will be recognized that the rate of application is dependent upon thespecies to be treated and the results desired. In general, rates of from0.25 to 20 kilograms per hectare are used although higher or lower ratescan achieve the desired effect in some instances.

The following examples are presented to further illustrate theformulation and application of the compounds of this invention. Partsand percentages in the following examples are by weight unless otherwiseindicated.

EXAMPLE 8 l A dust having the following formula is prepared.

Ammonium allyl carbamoylphosphonate 5.0% Talc 64.0% Attapulgite 30.0%Sodium benzenesulfonate 1.0%

The active component is ground with the minor diluent and the surfactantto pass a 0.149 mm. screen. This material is then blended with the majordiluent to form a dust composition.

It will be understood that the other compounds of this invention canalso be formulated in a like manner.

The dust formulation of Example 81 is applied, using a helicopter, at arate of kilograms per hectare to an area under an electric power line inwhich the brush and trees have been freshly trimmed inspring at the timewhen the leaves on most of the plants are just fully expanded. Theapplication is made in the early morning when the foliage is wet withdew or just after a rain; This treatment retards the growth of a largenumber of species along the right-of-way including the followingspecies: red maple (Acer rubrum), black willow (Salix EXAMPLE 82 Awater-soluble powder of the following formula is prepared.

Ammonium allyl carbamoylphosphonate 95.0% Synthetic silica 3.5% Disodiumhydrogen phosphate 1.0% Dioctylsodium sulfosuccinate 0.5%

The above ingredients are mixed and then ground to pass a 0.42 mm.screen. The resulting formulation is water-soluble powder, with theexception of the synthetic silica conditioning agent.

The following compounds of this invention can also be formulated in likemanner.

Ammonium 2-chloroethyl carbamoylphosphonate Ammonium methylcarbamoylphosphonate Sodium phenyl carbamoylphosphonate Hemicalciumbenzyl carbamoylphosphonate Hemibarium ethyl carbamoylphosphonateAmmonium 2,3-dibromopropyl carbamoylphosphonate Diethylammonium ethylcarbamoylphosphonate Ammonium hexyl carbamoylphosphonate Four kilogramsof the water-soluble powder formulation of Example 82 is dissolved in200 liters of water and 0.5 percent of a non-phytotoxic wetting agent isadded. This solution is sprayed on one hectare of freshly trimmed Norwaymaple (Acer plantanoides) growing along struts under a power line. Thistreatment greatly reduces the rate of growth of the trees and extendsthe time interval between trimmings. The trees are not significantlyinjured by the treatment.

The water-soluble powder of Example 82 can be dissolved in water at therate of 2,000 p,p.m. of active ingredient and applied to 1 acre ofVirginia bunch peanuts at the time they are beginning to flower. Thetreatment prevents excessive vegetative growth and promotes floweringand fruit set of the treated plants. As a result of the treatment theplants are easier to harvest and'dry and more high quality nuts areharvested.

Example 83 Ammonium ethyl carbamoylphosphonate 90% Silica aerogel 4%Sugar 6% The ingredients are combined, blended, crushed through a U.S.S.No. 20 sieve (0.84 mm. openings) and reblended.

In mid-September, active ingredient formulated as described above wasdissolved in water containing 0.2 percent sorbitan monolaurate andapplied to the foliage of red maple (Acer rubrum), sweet gum(Liquidambar styraciflua) and green briar (Smilax spp.) at the rate of 3kg/ha in 800 l. of water. The treatment had no apparent effect on theplants for the remainder of the season. However, the next July thetreated plants had developed almost no leaves.- What buds that hadbroken had produced only minute red-tinged leaves. Except for some tips,the bare branches were still alive. The floor beneath-the treated brushwas green with herbaceous vegetation.

Water EXAMPLE 84 A wettable powder of the following formula is prepared.

Hemibarium benzyl carbamoylphosphonate Montmorrilonite Synthetic silicaDisodium hydrogen phosphate Sodium alkylnaphthalenesulfonate Sodiumlignin sulfonate The above ingredients are mixed and then ground to passa 0.25 mm. screen. The active ingredient in the above formulationdissolves when the composition is added to water.

Twenty kilograms of the formulation of Example 84 t is added to 400liters of water and agitated until the active ingredient dissolves. Thissolution is then sprayed on 1 hectare of newly trimmed hedgerow in thespring after the leaves have expanded. This treatment greatly reducesthe growth of plants growing in the hedgerow such as osage orange(Maclura pomifera), but does not seriously injure them. The hedgerow isthus kept neat with a minimum of labor expended for trimming it.

EXAMPLE 85 A solution of the following formula is prepared.

Ammonium ethyl carbamoylphosphonate Disodium hydrogen phosphate Sodiumlaurylsulfate Water The above components are blended to form ahomogeneous solution.

The following compounds can be formulated in like manner. I 4

Benzyltrimethylammonium benzyl N,N-dimethylcarbamoylphosphonate ITrimethylammonium ethyl N-methylcarbamoylphosgrowth of the bluegrass fora period of 4 to 8 weeks and the mowing required to maintain the area inan tive condition is reduced.

EXAMPLE 86 A solution of the following formula is prepared.

attrac- Allylammonium allyl N,N-dimethylcarbamoyl- 24.0% phosphonateTrimethylpolyethyleneglycol ether 1.0% 20.0%

Ethylene Glycol 55.0%

A solution containing 227 gms. of active ingredient formulated as aboveis sprayed on an area of red delicious apple trees about 2 weeks afterpetal fall. This treatment prevents the June drop and gives a higheryield of apples per acre than that from a similar untreated acre oftrees. It also reduces the growth of spurious sheets known as watersprouts and ameliorates the tendency to biannual hearing which is strongin this variety.

EXAMPLE 87 The following formulation is prepared.

Ammonium methyl carbamoyphosphonate 25.0% Sodium lauryl sulfate 50.0%Magnesium silicate 10.0% Kaolinite 15.0%

The above components are blended, micropulverized to pass a 0.30 mm.screen and reblended.

The following compounds can be formulated in like manner.

Morpholinium ethyl carbamoylphosphonate Sodium phenylcarbamoylphosphonate Hemicalcium benzyl carbamoylphosphonate Fivekilograms of the formulation of Example 87 are suspended in 100 litersof water and then sprayed to runoff on freshly trimmed trees and brushalong the edge of a power line right-of-way. This treatment greatlyreduces the growth of the trees and shrubs without permanent injury tothem and they are prevented from growing over into the power line. Thevegetation on the right-of-way is controlled by applying herbicides.This treatment reduces the labor required to maintain the line.

EXAMPLE 88 An aqueous concentrate solution is prepared which containsthe following ingredients:

ammonium ethyl carbamoylphosphonate 24.0%

Ndimethylaminosuccinamic acid l2.0% water 32.0% methanol 32.0%

The above ingredients are stirred together with slight in earlySeptember. The treatment prevents coloration in the apples and preventspremature fall before the apples are harvested.

Example 89 Water The ingredients are combined and stirred to produce asolution containing approximately 4 pounds active ingredient per gallon(480 g. per liter). After filtration through a bed of diatomaceousearth, the product is packed in glass or plastic containers until use.

IriSe pte mb er, oaks (Qu ercus sppfl), hickory (Carvd 1 spp.) andLoblolly pine (Pinus taeda) were treated with a foliar spray of theabove formulation at the rate of 6 kg/ha in 800 liters of water. Thetreated plants showed no response that fall but next spring thedeciduous spe cies failed to develop new leaves and the pine did notdevelop new shoots. The treatment had prevented the new buds frombreaking in the spring although plant stems and limbs were observed tobe alive when examined closely.

EXAMPLE 90 The following wettable powder is prepared:

ammonium ethyl carbamoylphosphonate 30.0% maleic hydrazide 20.0%synthetic silica 2.5% montmorillonite 45.0% sodium alkylnaphthalenesulfonate 2.0% partially desulfonated sodium lignin sulfonate 0.5%

The above ingredients are blended, micropulverized to a particle sizeessentially below 50 microns and re blended.

The wettable powder of Example 90 is suspended in water at the rateof'4,000 p.p.m. of active ingredient and sprayed on an area of mixedbrush under a power line. The application is made in mid-May just afterthe brush has been trimmed back to keep it away from under the powerline. The solution is sprayed to run-off on the lower two-thirds of thetrees which were not cut. This treatment effectively retards the growthof the trimmed vegetation for the next growing season as well as the onein which the vegetation is treated.

The formulation of Example 90 is suspended in water at the rate of 1,000p.p.m. of active ingredient and sprayed to the point of run-off onsingle trees located at random throughout orchards of apple, peach andcherry varieties. The treatments are applied while the trees are stillin the dormant stage. During an early EXAMPLE 91 The following aerosolpreparation is prepared:

(ammonium ethyl carbamoylphosphonate 1.0%

( water 29.0%

' (asphalt 20.0%

B lxylene 25.0%

-Continued polyglycerol stearate dic 20.0%

C i hloro difluoromethane The predissolved aqueous phase (A), comprisingactive ingredient in water, is combined with the organic phase (B),comprising a solution of asphalt, emulsifier, and xylene, withagitation. To this is added, under pressure in an aerosol dispenser, thepropellant C.

Trees under a power line are trimmed back in early May to prevent themgrowing into the lines. The cut ends are treated with the wound dressingdescribed above. The treatment reduces the break of lateral buds andretards the rate of growth of those that do break. In addition, thetreatment causes overall retardation in the rate of growth of thetreated plants. This lengthens the time between trimmings, reducing thecost of maintaining the power line. Trees treated include sweetgum(Liquidambar styraciflua L.), black willow (Salix nigra Marsh.), apple(Malus sp. Mill.), and red maple (Acer rubrum L.).

EXAMPLE 92 The following asphalt emulsion is prepared:

ammonium ethyl carbamoylphosphonate 4.0% sodium oleate 2.0% water I47.0% asphalt 47.0%

The active compound, sodium oleate and water are combined and heated to90C. In a high' shear mixer,

maple (Acer saccharum Marsh.), growing under a power line. The treatmentretards the breaking of lateral buds and the rate of growth of laterals.This remolten asphalt is added. The suspension is cooled and duces thefuture trimming necessary to maintain the area.

I claim: 1

l. A compound of the formula:

IULN

where R is alkyl of one through four carbon atoms, or alkenyl of threethrough four carbon atoms, R and R are each hydrogen; and

M is ammonium, hydrogen, sodium, lithium 'or potassium.

3. Ammonium allyl carbamoylphosphonate.

4. Ammonium ethyl carbamoylphosphonate.

5. Ammonium isopropyl carbamoylphosphonate.

1. A COMPOUND OF THE FORMULA:
 2. A compound of the formula:
 3. Ammoniumallyl carbamoylphosphonate.
 4. Ammonium ethyl carbamoylphosphonate. 5.Ammonium isopropyl carbamoylphosphonate.